Nothing Special   »   [go: up one dir, main page]

EP2610272B1 - Composant de catalyseur - Google Patents

Composant de catalyseur Download PDF

Info

Publication number
EP2610272B1
EP2610272B1 EP11196164.5A EP11196164A EP2610272B1 EP 2610272 B1 EP2610272 B1 EP 2610272B1 EP 11196164 A EP11196164 A EP 11196164A EP 2610272 B1 EP2610272 B1 EP 2610272B1
Authority
EP
European Patent Office
Prior art keywords
compound
group
metal
catalyst
catalyst component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP11196164.5A
Other languages
German (de)
English (en)
Other versions
EP2610272A1 (fr
Inventor
Peter Denifl
Timo Leinonen
Georgy Kipiani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borealis AG
Original Assignee
Borealis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Borealis AG filed Critical Borealis AG
Priority to EP11196164.5A priority Critical patent/EP2610272B1/fr
Priority to PCT/EP2012/076052 priority patent/WO2013098138A1/fr
Publication of EP2610272A1 publication Critical patent/EP2610272A1/fr
Application granted granted Critical
Publication of EP2610272B1 publication Critical patent/EP2610272B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene

Definitions

  • the invention relates to a particulate olefin polymerisation catalyst component, particularly one comprising a Group 2 metal and to a process for preparing same.
  • the invention also relates to an olefin polymerization catalyst comprising particles of the catalyst component and to the use of such a catalyst for the polymerisation of olefins.
  • ZN type polyolefin catalysts are well known in the field of polymers, generally, they comprise (a) at least a catalyst component formed from a transition metal compound of Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 1989), a metal compound of Group 1 to 3 of the Periodic Table (IUPAC), and, optionally, a compound of group 13 of the Periodic Table (IUPAC) and/or an internal donor compound.
  • ZN catalyst may also comprise (b) further catalyst component(s), such as a cocatalyst and/or an external donor.
  • Various methods for preparing ZN catalysts are known in the state of art.
  • a supported ZN catalyst system is prepared by impregnating the catalyst components on a particulate support material.
  • the catalyst component(s) are supported on a porous, inorganic or organic particulate carrier material, such as silica.
  • the carrier material is based on one of the catalyst components, e.g. on a magnesium compound, such as MgCl 2 .
  • This type of carrier material can also be formed in various ways.
  • EP-A-713 886 of Japan Olefins describes the formation of MgCl 2 adduct with an alcohol which is then emulsified and finally the resultant mixture is quenched to cause the solidification of the droplets.
  • EP-A-856 013 of BP discloses the formation of a solid Mg-based carrier, wherein the Mg-component containing phase is dispersed to a continuous phase and the dispersed Mg-phase is solidified by adding the two-phase mixture to a liquid hydrocarbon.
  • the formed solid carrier particles are normally treated with a transition metal compound and optionally with other compounds for forming the active catalyst. Accordingly, in case of external carriers, some examples of which are disclosed above, the morphology of the carrier is one of the defining factors for the morphology of the final catalyst.
  • One disadvantage encountered with the supported catalyst systems is that distribution of the catalytically active compounds on the support material is highly dependent on the support particle structure, like compactness of the support particles, porosity and pore size distribution. As a result this may often lead to non-uniform distribution of the active component(s) within the catalyst particle.
  • WO-A-00 08073 and WO-A-00 08074 describe further methods for producing a solid ZN catalyst, wherein a solution of an Mg-based compound and one or more further catalyst compounds are formed and the reaction product thereof is precipitated out of the solution by heating the system.
  • EP-A-926 165 discloses another precipitating method, wherein a mixture of MgCl 2 and Mg-alkoxide is precipitated together with a Ti-compound to give a ZN catalyst.
  • a magnesium compound, an alcohol, an ether, a surfactant and an alkyl silicate are reacted first to get a catalyst support, which is then further reacted with a titanium compound.
  • the solid titanium catalyst component is obtained via precipitation.
  • the catalyst component further comprises an internal donor, which can be selected form a great variety of compounds.
  • WO 03/000757 as well WO 03/000754 describe a process for the preparation of an olefin polymerisation catalyst component, enabling to prepare solid particles of a catalyst component comprising a group 2 metal together with a transition metal however without using any external carrier material or without using conventional precipitation methods, but using so called emulsification-solidification method for producing solid catalyst particles.
  • a phthalate type internal electron donor is prepared in situ during the catalyst preparation in a way and using chemicals so that an emulsion is formed. Droplets of the dispersed phase of the emulsion form the catalyst component, and solidifying the droplets results in solid particulate catalyst.
  • WO 2004/029112 discloses a further modification of the emulsion-solidification method as described in WO 03/000757 as well WO 03/000754 , and relates thus to process for preparing an olefin polymerisation catalyst component, wherein the process is further characterized in that a specific aluminum alkyl compound is brought into contact with the catalyst component, enabling a certain degree of activity increase at higher temperatures.
  • EP 0 018 738 relates to a solid titanium catalyst component for use in the production of olefin polymers or copolymers comprising titanium, magnesium, halogen and an electron donor as essential ingredients, and further comprising an inert liquid hydrocarbon in an amount of, based on the weight of said component, 1 to 10% when that component has a uniformity coefficient of at least 4, and 1 to 25% when that component has a uniformity coefficient of less than 4.
  • US 2005/0288460 discloses catalyst systems and method for making the catalyst systems/supports for the polymerisation of polyethylene containing a solid titanium catalyst component containing a titanium compound and support made of a magnesium compound, an alkyl silicate, and a monoester.
  • EP 0 159 736 describes a free-flowing olefin polymerisation procatalyst component prepared by the addition of limited amounts of a mineral oil to a recovered MgCl 2 /TiCl 4 /electron donor procatalyst.
  • a further aspect of the present invention is the desire to avoid as far as possible the use of substances which are considered as potential harmful compounds regarding health as well as environmental aspects.
  • One class of substances which have been considered as potential harmful compounds is phthalates, which have been commonly used as internal electron donors in Ziegler-Natta type catalysts. Although the amount of these phthalate compounds, used as internal donors in catalysts, in the final polymer is very small, it is still desirable to find out alternative compounds to replace phthalate compounds and still get catalysts having good activity, excellent morphology resulting in the desired polymer properties.
  • non-phthalate donors are as such not new in ZN catalysts.
  • such donors are mainly used in catalysts, which are prepared by supporting the catalyst components on an external carrier.
  • Drawbacks of such catalysts are described above.
  • the catalyst component has desired morphology.
  • a method for preparing solid catalyst components which allows the formation of the catalyst components in different ways (e.g. precipitation or emulsion/solidification method) but with a common mechanism and which further does not require the use of phthalates as internal electron donor, yielding catalyst components of desired chemical composition, morphology and particle size, which are suitable for producing polymers with the desired polymer properties.
  • benzoic acid esters or alkylene glycol dibenzoates suitable as internal donor show high chemical stability and are therefore less prone to undergo transesterificiation/decomposition during catalyst preparation than other phthalate free internal donors, like optionally substituted maleates.
  • benzoic acid esters or alkylene glycol dibenzoates - based catalysts show an improved hydrogen response compared to other ZN-catalysts, especially compared to phthalate - based catalysts, which allows the production of higher MFR products with lower amounts of hydrogen than with catalysts of prior art.
  • a copolymer, produced with a catalyst of the invention with a randomness being at least ⁇ 3% lower than for copolymers produced with a catalyst using as internal donor phthalate type donors at the same comonomer content is desired in order to achieve the desired properties for the polymer, like stiffness.
  • the present invention provides a process for preparing an olefin polymerisation catalyst component in the form of solid particles comprising the steps of
  • the present invention provides particles of the catalyst component obtainable according to the above process.
  • the present invention also provides an olefin polymerisation catalyst comprising particles of the above catalyst component and a co-catalyst, preferably an alkyl aluminum co-catalyst and optionally an external electron donor, as well as the use of said catalyst for polymerising olefins, in particular C 2 to C 10 ⁇ -olefins, preferably ethylene or propylene optionally with co-monomers, selected from C 2 to C 12 monomers.
  • olefin polymerisation catalyst comprising particles of the above catalyst component and a co-catalyst, preferably an alkyl aluminum co-catalyst and optionally an external electron donor, as well as the use of said catalyst for polymerising olefins, in particular C 2 to C 10 ⁇ -olefins, preferably ethylene or propylene optionally with co-monomers, selected from C 2 to C 12 monomers.
  • the present specification describes a solid catalyst component with
  • the present invention provides the catalysts obtainable in accordance with the present invention and further use of the catalysts in the olefin polymerisation.
  • solid catalyst components can be prepared via liquid/liquid two-phase (emulsion) system - solidification method or via precipitation method without the need of using phthalate compounds leading to catalyst particles having desired physical properties, e.g. especially desired morphological properties and/or desired particle size and particle size distribution.
  • catalyst component particles having in embodiments desired morphology and/or particle size and/or particle size distribution can be obtained by the emulsion-solidification or precipitation way of preparing Ziegler-Natta (ZN) type catalysts, which are suitable for use in olefin polymerisation, in particular for propylene polymerisation, but not requiring the use of phthalates.
  • ZN Ziegler-Natta
  • the chemical composition of the catalysts of the invention differ from the one of the closest prior art. According to the replica effect, the polymer particles produced by using the inventive catalyst have desired morphological properties, too.
  • the inventive catalyst preparation is based on a liquid/liquid two-phase system (emulsion/solidification method) or on a precipitation method where no separate external carrier materials such as silica or MgCl 2 are needed in order to get solid catalyst particles.
  • This process for preparing solid catalyst particles is in particular characterized in that the formation of the catalyst component comprises use of at least one alkoxy compound (Ax) being the reaction product of at least one compound of Group 2 metal and at least a monohydric alcohol (A) and at least one alkoxy compound (Bx) being the reaction product of at least one compound of Group 2 metal and an alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, or of at least one alkoxy compound (Ax) being the reaction product of at least one compound of Group 2 metal and a mixture of monohydric alcohol (A) with a further alcohol (B) comprising in addition to the hydroxy! moiety at least one further oxygen bearing group being different to a hydroxyl moiety, in an organic liquid reaction medium and further characterized that phthalate free internal electron donors based on benzoates or dibenzoates are used in the catalyst preparation as such or formed in situ.
  • the alkoxy compound (Ax) is a reaction product of at least one compound of Group 2 metal and a monohydric alcohol (A) or a reaction product of at least one compound of Group 2 metal and a mixture of monohydric alcohol (A) with a further alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety.
  • At least one alkoxy compound (Ax) being a reaction product of at least one compound of Group 2 metal and a monohydric alcohol (A) it is possible to use at least one additional alkoxy compound (Bx) being a reaction product of at least one compound of Group 2 metal and an alcohol comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, as defined below (alcohol B).
  • the alkoxy compounds (Ax and Bx) can be prepared in situ in the first step of the catalyst preparation process by reacting said compounds of Group 2 metal with the alcohol or alcohol mixture as described above, or said alkoxy compounds can be separately prepared reaction products, or they can be even commercially available as ready compounds and used as such in the catalyst preparation process of the invention.
  • a donor or a donor precursor can be added into the reaction mixture, whereby a Group 2 metal complex (Complex Ac or Bc) is formed, which is defined in this application to be a complex of at least the Group 2 metal compound, the alcohol or alcohol mixture and a donor.
  • a Group 2 metal complex (Complex Ac or Bc) is formed, which is defined in this application to be a complex of at least the Group 2 metal compound, the alcohol or alcohol mixture and a donor.
  • alkoxy compounds (Ax) and/or (Bx) are formed without using any donor(s) or donor precursor(s), donor(s) as such is added separately to the reaction product solution or during preparation of the catalyst component.
  • Group 2 metal is selected from the group comprising, preferably consisting of Group 2 metal dialkyls, alkyl Group 2 metal alkoxides, alkyl Group 2 metal halides and Group 2 metal dihalides. It can further be selected from the group consisting of dialkyloxy Group 2 metal, diaryloxy Group 2 metal, alkyloxy Group 2 metal halides, aryloxy Group 2 metal halides, alkyl Group 2 metal alkoxides, aryl Group 2 metal alkoxides and alkyl Group 2 metal aryloxides.
  • Group 2 metal is magnesium.
  • Monohydric alcohols (A) are those of formula ROH in which R is a linear or branched C 1 -C 20 alkyl.
  • Typical C 1 -C 5 monohydric alcohols are methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec.butanol, tert.butanol, n-amyl alcohol, iso-amyl alcohol, sec. amyl alcohol, tert. amyl alcohol, diethyl carbinol, sec. isoamyl alcohol, tert. butyl carbinol.
  • Typical C 6 -C 10 monohydric alcohols are hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutyl carbinol, 1-decanol and 2,7-dimethyl-2-octanol.
  • Typical >C 10 monohydric alcohols are n-1-undecanol, n-1-dodecanol, n-1-tridecanol, n-1-tetradecanol, n-1-pentadecanol,1-hexadecanol, n-1-heptadecanol and n- 1 octadecanol.
  • the monohydric alcohols may be unsaturated, as long as they do not act as catalyst poisons.
  • Preferable monohydric alcohols are those of formula ROH in which R is a C 2 -C 16 alkyl group, most preferably a C 4 -C 12 alkyl group, particularly 2-ethyl-1-hexanol.
  • Alcohol (B) is an alcohol which comprises in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety
  • Such further oxygen bearing group is an ether moiety.
  • the alcohol (B) as defined above may be aliphatic or aromatic although aliphatic compounds are preferred.
  • the aliphatic compounds may be linear, branched or cyclic or any combination thereof and in particular preferred alcohols are those comprising one ether moiety.
  • Illustrative examples of such preferred ether moiety containing alcohols (B) to be employed in accordance with the present invention are glycol monoethers, in particular C 2 to C 4 glycol monoethers, such as ethylene or propylene glycol monoethers wherein the ether moieties comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms.
  • Preferred monoethers are C 2 to C 4 glycol monoethers and derivatives thereof.
  • Illustrative and preferred examples are ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol 2-ethylhexyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-hexyl ether, propylene glycol 2-ethylhexyl ether, with ethylene glycol hexyl ether, 1,3-propylene glycol ethyl ether and 1,3-propylene glycol n-butyl ether, being particularly preferred.
  • the most preferred alcohol (B) is 1,3-propylene glycol n-butyl ether.
  • the different complexes or alcohols are usually employed in a mole ratio of from 10:1 to 1:10, preferably this mole ratio is from 8:1 to 1:8, more preferably 6:1 to 1:6, even more preferably 4:1 to 1:4 and in embodiments also 2:1 to 1:2.
  • This ratio can be adjusted depending on the used donor e.g. donors with short chains require longer chain alcohols and vice versa.
  • the reaction for the preparation of the alkoxy compounds (Ax) and (Bx) may in embodiments, be carried out preferably in an aromatic or aromatic/aliphatic medium at a temperature of 20° to 80°C, and in case that the Group 2 metal is magnesium, the preparation of the alkoxy magnesium compound may be carried out at a temperature of 50° to 70°C.
  • the reaction medium used as solvent can be aromatic or a mixture of aromatic and aliphatic hydrocarbons, the latter one containing 5 - 20 carbon atoms, preferably 5 - 16 carbon atoms more preferably 5 - 12 carbon atoms and most preferably 5 to 9 carbon atoms.
  • the aromatic hydrocarbon is selected substituted and unsubstituted benzenes, preferably from alkylated benzenes, even more preferably from toluene and xylenes, and is most preferably toluene.
  • the molar ratio of said reaction medium to magnesium is preferably less than 10, for instance from 4 to 10, preferably from 5 to 9.
  • Alkoxy compounds (Ax) and (Bx) are preferably alkoxy magnesium compounds.
  • the alkoxy magnesium compound is preferably selected from the group consisting of magnesium dialkoxides, complexes of a magnesium dihalide and an alcohol, and complexes of a magnesium dihalide and a magnesium dialkoxide, more preferably the alkoxy magnesium compound is a magnesium dialkoxide compound.
  • the alkoxy magnesium compound is the reaction product of the alcohol (A) respectively alcohol (B) or a,mixture of alcohol (A) and alcohol (B) with a magnesium compound selected from the group consisting of dialkyl magnesiums, alkyl magnesium alkoxides, alkyl magnesium halides and magnesium dihalides. It can further be selected from the group consisting of dialkyloxy magnesiums, diaryloxy magnesiums, alkyloxy magnesium halides, aryloxy magnesium halides, alkyl magnesium alkoxides, aryl magnesium alkoxides and alkyl magnesium aryloxides.
  • the magnesium dialkoxide is may be the reaction product of dialkyl magnesium of the formula R 2 Mg, wherein each one of the two Rs is a similar or different C 1 -C 20 alkyl, preferably a similar or different C 2 -C 10 alkyl, and alcohol A respectively B.
  • Typical magnesium alkyls are ethylbutyl magnesium, dibutyl magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl magnesium, butylpentylmagnesium, butyloctyl magnesium and dioctyl magnesium.
  • one R of the formula R 2 Mg is a butyl group and the other R is an ethyl or octyl group, i.e. the dialkyl magnesium compound is butyl octyl magnesium or ethyl butyl magnesium.
  • Typical alkyl-alkoxy magnesium compounds RMgOR when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide.
  • the electron donor compound used in the preparation of the catalyst of the present invention is selected from benzoates of formula (I). and alkylene glycol dibenzoates selected from ethylene glycol dibenzoate 1,2-propylene glycol dibenzoate and 1,3-propylene glycol dibenzoate, or a corresponding precursor.
  • the C 6 -C 14 -aryl group is preferably a phenyl group
  • the optional substituents on the aryl group can be linear or branched C 1 -C 12 -alkyl, preferably linear or branched C 1 -C 10 -alkyl and more preferably linear or branched C 1 -C 8 -alkyl or halogen, like chlorine, fluorine or bromine, preferably chlorine or bromine and more preferably chlorine.
  • the number of substituents on the aryl group can be 0 to 4, preferably 0 to 2, more preferably 0 or 1.
  • R' being not H can be in ortho- meta or para position, preferably in para or ortho-position.
  • More preferred compounds of formula (I) are 2-ethylhexyl benzoate, 2-ethylhexyl (4-n-hexylbenzoate), 2-ethylhexyl (4-tert.-butylbenzoate), 2-ethylhexyl ((2-(4-chlorobenzoyl)benzoate).
  • Preferred compounds of the formula (II) are ethylene glycol dibenzoate, 1,2-propylene glycol dibenzoate and 1,3-propylene glycol dibenzoate.
  • the electron donor may also be used in the form of a suitable precursor, preferably in the form of the corresponding halides, more preferably chlorides. It is also possible to use mixtures of the above described donors.
  • the compound of a transition metal is preferably a compound of a Group 4 metal.
  • the Group 4 metal is preferably titanium, and its compound to be reacted with the complex of a Group 2 is preferably a halide.
  • Equivalent to titanium tetrahalide is the combination of an alkoxy titanium halide and a halogenation agent therefore, which are able to form a titanium tetrahalide in situ.
  • the most preferred halide is the chloride.
  • a compound of a transition metal used in the process can also contain organic ligands typically used in the field known as a single site catalyst.
  • a compound of a transition metal can also be selected from Group 5 metals, Group 6 metals, Cu, Fe, Co, Ni and/or Pd compounds.
  • said olefin polymerisation catalyst components can be obtained in several ways all based on the same mechanism.
  • step (a1) it is possible to use an alkoxy compound (Ax) being a reaction product of at least one Group 2 metal compound and a mixture of alcohol (A) with alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, as defined above.
  • a further possibility is to use a mixture of an alkoxy compound (Ax) being a reaction product of at least one Group 2 metal compound and a monohydric alcohol (A) and an alkoxy compound (Bx) being a reaction product of at least one Group 2 metal compound and an alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, as defined above.
  • the process of solids precipitation can be carried out by several methods:
  • the addition of solution (S1) to the at least one transition metal compound (CT) in step (b1) is done at a temperature of at least 50 °C, preferably in the temperature range of 50 to 110 °C, more preferably in the range of 70 to 100 °C, most preferably in the range of 85 to 95 °C, at which temperature the at least one transition metal compound (CT) is in a liquid form, resulting in the precipitation of said solid catalyst components.
  • the whole reaction mixture is kept at least at 50°C, more preferably is kept in the temperature range of 50 to 110 °C, more preferably in the range of 70 to 100 °C, most preferably in the range of 85 to 95 °C, to secure full precipitation of the catalyst component in form of a solid particle.
  • surfactants include polymer surfactants, such as poly(alkyl methacrylate) and poly(alkyl acrylate), and the like.
  • a polyalkyl methacrylate is a polymer that may contain one or more methacrylate monomers, such as at least two different methacrylate monomers, at least three different methacrylate monomers, etc.
  • the acrylate and methacrylate polymers may contain monomers other than acrylate and methacrylate monomers, so long as the polymer surfactant contains at least about 40% by weight acrylate and methacrylate monomers.
  • surfactants examples include those under the trade marks VISCOPLEX (R) available from RohMax Additives, GmbH, especially those having product designations 1-254, 1-256 and those under the trade designations CARBOPOL (R) and PEMULEN (R) available from Noveon/Lubrizol.
  • the solution (S1) is mixed with at least one transition metal compound (CT) in liquid form at a temperature of about -20°C to about 30°C and precipitating the solid catalyst components by subsequently slowly raising the temperature to at least 50 °C, preferably in the temperature range of 50 to 110 °C, more preferably in the range of 70 to 100 °C, most preferably in the range of 85 to 95 °C, whereby the rate of temperature increase is in the range from 0.1 °C to 30°C per minute, preferably 0.5 to 10°C per minute.
  • CT transition metal compound
  • a surfactant is added to the solution (S1) before step (b1). Suitable surfactants are described above.
  • a precipitating agent according to this invention is an agent which promotes the precipitation of the catalyst component in form of a solid particle.
  • the organic liquid medium used as (OM2), as defined later in this application, can promote the precipitating and thus act and used as a precipitating agent.
  • the final catalyst does not contain any such medium.
  • no precipitating agent has been used in the process as stated above.
  • the catalyst component as prepared in the previous paragraphs is a precipitated solid particle.
  • Precipitation means that during the catalyst component preparation a chemical reaction in a solution takes place leading to the desired catalyst component insoluble in said solution.
  • Suitable electron donors and their precursors as well as suitable transition metal compounds are also described above.
  • TiCl 4 is used as transition metal compound.
  • the electron donor is added to alkoxy compound (Ax), or alkoxy compound (Bx) if present, or to the mixture of the alkoxy compound (Ax) and (Bx), obtained by mixing alkoxy compound (Ax) being a reaction product of at least one Group 2 metal compound as described above with the monohydric alcohol (A) as described above and alkoxy compound (Bx) being a reaction product of at least one Group 2 metal compound as described above and the alcohol (B), as described above, whereby the reaction medium used as solvent for the Group 2 metal compound can be aromatic or a mixture of aromatic and aliphatic hydrocarbons, the latter one containing 5 - 20 carbon atoms, preferably 5 - 16 carbon atoms more preferably 5 - 12 carbon atoms and most preferably 5 to 9 carbon atoms.
  • the aromatic hydrocarbon is selected substituted and unsubstituted benzenes, preferably from alkylated benzenes, even more preferably from toluene and xylenes, and is most preferably toluene.
  • the electron donor can also be introduced in form of a precursor, like optionally substituted benzoyl chloride, which is then transformed in situ to the electron donor by reaction with a corresponding Mg-alkoxide.
  • a precursor like optionally substituted benzoyl chloride
  • the corresponding alkoxide is prepared as described above by reacting a magnesium compound with the corresponding alcohol (A) and/or (B).
  • Additional donors can be added, if so desired into the catalyst preparation in any of steps (a1) to (c1).
  • additional donors if used, are non-phthalic acid ester as well. It is also possible to use mixtures of the above described donors.
  • the reaction medium corresponds to the organic liquid reaction medium (OM1) of step (a1).
  • the organic liquid reaction medium (OM2) where TiCl 4 can be solved, can be the same as the organic liquid reaction medium (OM1) or can be different thereto, the latter being preferred.
  • the organic liquid reaction medium (OM2) is C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 alkane, like heptane, octane or nonane, or any mixtures thereof.
  • the organic liquid reaction medium (OM1) is a C 6 to C 10 aromatic hydrocarbon, most preferably toluene
  • the organic liquid reaction medium (OM2) is a C 6 to C 10 alkane, most preferably heptane.
  • organic liquid reaction media (OM1) and (OM2) are selected in a way which supports the immediate precipitation of the solid catalyst particle.
  • Suitable mixing techniques include the use of mechanical as well as the use of ultrasound for mixing, as known to the skilled person.
  • solid catalyst particle is washed at least once up to 6 times, preferably at least twice, most preferably at least three times with a hydrocarbon, which preferably is selected from aromatic and aliphatic hydrocarbons, preferably with toluene, heptane or pentane, more preferably toluene, particularly with hot (e.g. 80 to 100°C) toluene, which might include a smaller or higher amount of TiCl 4 in it.
  • the amount of TiCl 4 can vary from a few vol% to more than 50-vol%, such as from 5-vol% to 50-vol%, preferably from 5 to 15-vol%. It is also possible that at least one wash is done with 100-vol% TiCl 4 .
  • One or several further washes after aromatic and/ or TiCl 4 washes can be run with aliphatic hydrocarbons of 4 to 8 carbon atoms. Preferable these latter washings are performed with heptane and/or pentane. Washings can be done with hot (e.g. 90°C) or cold (room temperature) hydrocarbons or combinations thereof. It is also possible that all washings will be done with the same solvent, e.g. toluene.
  • a reducing agent which decreases the amount of titanium present in said solidified particles of the olefin polymerisation catalyst component being present in the oxidation state +4, can be added.
  • Suitable reducing agents are aluminium alkyl compounds, aluminium alkyl alkoxy compounds as well as magnesium compounds as defined in the present specification.
  • Suitable aluminium compounds have a general formula AlR 3-n X n , wherein R stands for a straight chain or branched alkyl or alkoxy group having 1 to 20, preferably 1 to 10 and more preferably 1 to 6 carbon atoms, X independently represents a residue selected from the group of halogen, preferably chloride, and n stands for 0, 1 or 2. At least one of the R residues has to be an alkyl group.
  • the compound can be added as an optional compound to the catalyst component synthesis and can be added at any step (b1) to (c1), or during the washing step as described above, however, before step (d1).
  • the reducing compound is added during the washing step, more preferably during the first washing step with hot toluene.
  • aluminium alkyl and alkoxy compounds to be employed in accordance with the present invention are:
  • Suitable magnesium compounds are magnesium compounds as defined herein in connection with the complex of a Group 2 metal. The respective disclosure is incorporated herein by reference with respect to the magnesium compound to be added in accordance with the process of the present invention.
  • suitable magnesium compounds are dialkyl magnesium compounds or halogenated alkyl magnesium compounds of the general formula MgR 2-n X n , where each n is 0 or 1, and each R are same or different alkyl groups with 1 to 8 carbon atoms and X is halogen, preferably Cl.
  • One preferred magnesium compound is butyloctyl magnesium (commercially available under the trade name BOMAG), which is already preferably used in the preparation of the Mg alkoxy compound, respectively Mg complex.
  • the added amount of the optional Al compound depends on the desired degree of reduction of amount of titanium present in the solidified particles of the olefin polymerisation catalyst component being present in the oxidation state +4.
  • the preferred amounts of Al in the catalyst component depend to some extent on the Al compound, e.g. if an Al alkoxy compound is used, the preferred final Al amounts seem to be lower than if e.g. Al alkyl chloride compounds are used.
  • the final catalyst component particles have an Al content of 0.0 to 0.8 wt%, preferably 0.0 to 0.5 wt% or 0.0 to 0.4 wt%.
  • the magnesium compound to be added in accordance with the present invention is added in corresponding amounts.
  • a chlorinated aluminium alkyl compounds especially diethyl aluminium chloride; is added.
  • step (a2) it is possible to use an alkoxy compound (Ax) being a reaction product of at least one Group 2 metal compound and a mixture of alcohol (A) with alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, as defined above.
  • a further possibility is to use a mixture of an alkoxy compound (Ax) being a reaction product of at least one Group 2 metal compound and a monohydric alcohol (A) and an alkoxy compound (Bx) being a reaction product of at least one Group 2 metal compound and an alcohol (B) comprising in addition to the hydroxyl moiety at least one further oxygen bearing group being different to a hydroxyl moiety, as defined above.
  • Suitable electron donors and their precursors as well as suitable transition metal compounds are also described above.
  • the solution (S1) is typically a solution of at least one alkoxy compound (Ax) and an alkoxy compound (Bx) in liquid hydrocarbon reaction medium, which can be provided in situ by reacting an alcohol (A) or a mixture of alcohol (A) and alcohol (B) with the Group 2 metal compound in a liquid hydrocarbon medium to form alkoxy compound (Ax), as described above, and optionally mixing alkoxy compound (Ax) with alkoxy compound (Bx), prepared by reacting an alcohol (B) with the Group 2 metal compound in a liquid hydrocarbon medium.
  • the internal donor or precursor thereof as defined above is added preferably in step (a2) to said solution (S1). If the electron donor is used as such, it is added to alkoxy compound (Ax), or alkoxy compound (Bx) or to the mixture of the alkoxy compounds (Ax) and (Bx).
  • the electron donor can also be introduced in form of a precursor, like optionally substituted benzoyl chloride, which is then transformed in situ to the electron donor by reaction with a corresponding Mg-alkoxide.
  • the corresponding alkoxide is prepared as described above by reacting a magnesium compound with the corresponding alcohol.
  • step (a2) is then typically added to the at least one compound of a transition metal, such as titanium tetrachloride.
  • a transition metal such as titanium tetrachloride.
  • This addition preferably is carried out at a low temperature, such as from -10 to 40°C, preferably from -5 to 30°C, such as about 0°C to 25°C.
  • an organic reaction medium or solvent may be present, typically selected among aromatic and/or aliphatic hydrocarbons as described above.
  • Additional donors can be added, if so desired into the catalyst preparation in any of steps (a2) to (c2).
  • additional donors if used, are non-phthalic acid ester as well. It is also possible to use mixtures of the above described donors.
  • the process in accordance with the present invention yields as intermediate stage, as identified above an emulsion of a denser, transition metal compound/toluene-insoluble, oil dispersed phase typically having a transition metal metal/Group 2 mol ratio of 0.1 to 10 in an oil disperse phase having a transition metal/Group 2 mol ratio of 10 to 100.
  • Transition metal compound is preferably Group 4 metal compound, and is most preferably TiCl 4 .
  • Group 2 metal is preferably Mg.
  • This emulsion is then typically agitated, optionally in the presence of an emulsion stabilizer and/or a turbulence minimizing agent, in order to maintain the droplets of said dispersed phase, typically within an average size range of 2 to 500 ⁇ m.
  • the catalyst particles are obtained after solidifying said particles of the dispersed phase e.g. by heating.
  • the said disperse and dispersed phases are thus distinguishable from one another by the fact that the denser oil, if contacted with a solution of Group 4 metal compound preferably TiCl 4 in toluene, will not dissolve in it.
  • a suitable solution for establishing this criterion would be one having a toluene mol ratio of 0.1 to 0.3. They are also distinguishable by the fact that the great preponderance of the Mg provided (as complex) for the reaction with the Group 4 metal compound is present in the dispersed phase, as revealed by comparison of the respective Group 4 metal/Mg mol ratios.
  • the production of a two-phase reaction product is encouraged by carrying out the Mg complex/Group 4 metal compound reaction at low temperature, specifically above -10°C but below 50°C, preferably between above -5°C and below 40°C. Since the two phases will naturally tend to separate into a lower, denser phase and supernatant lighter phase, it is necessary to maintain the reaction product as an emulsion by agitation, preferably in the presence of an emulsion stabilizer.
  • the emulsion i.e. the two phase liquid-liquid system may be formed in all embodiments of the present invention by simple stirring and optionally adding (further) solvent(s) and additives, such as the turbulence minimizing agent (TMA) and/or the emulsifying agents described further below.
  • Emulsifying agents/emulsion stabilizers can be used additionally in a manner known in the art for facilitating the formation and/or stability of the emulsion.
  • surfactants e.g. a class based on acrylic or methacrylic polymers can be used.
  • said emulsion stabilizers are acrylic or methacrylic polymers, in particular those with medium sized ester side chains having more than 10, preferably more than 12 carbon atoms and preferably less than 30, and preferably 12 to 20 carbon atoms in the ester side chain.
  • Particular preferred are unbranched C 12 to C 20 (meth)acrylates such as poly(hexadecyl)-methacrylate and poly(octadecyl)-methacrylate.
  • Suitable examples of commercially available surfactants are e.g. those sold under the name of Viscoplex®, like Viscoplex®,1-124 and 1-126, as indicated earlier in this application.
  • a turbulence minimizing agent can be added to the reaction mixture in order to improve the emulsion formation and maintain the emulsion structure.
  • Said TMA agent has to be inert and soluble in the reaction mixture under the reaction conditions, which means that polymers without polar groups are preferred, like polymers having linear or branched aliphatic carbon backbone chains.
  • Said TMA is in particular preferably selected from alpha-olefin polymers of alpha-olefin monomers with 6 to 20 carbon atoms, like polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable it is polydecene.
  • TMA can be added to the emulsion in an amount of e.g. 1 to 1.000 ppm, preferably 5 to 100 ppm and more preferable 5 to 50 ppm, based on the total weight of the reaction mixture.
  • the ratio of the mol ratio Group 4 metal/Mg in the disperse phase oil to that in the denser oil is at least 10.
  • Solidification of the dispersed phase droplets by heating is suitably carried out at a temperature of 70 to 150°C, usually at 80 to 110°C, preferably at 90 to 110°C.
  • reaction mixture For isolating the solidified particles the reaction mixture is allowed to settle and the solidified particles are recovered from this reaction mixture for example by syphoning or by an in-stream filtering unit.
  • the solidified particulate product may be washed at least once up to 6 times, preferably at least twice, most preferably at least three times with a hydrocarbon, which preferably is selected from aromatic and aliphatic hydrocarbons, preferably with toluene, heptane or pentane, more preferably toluene, particularly with hot (e.g. 80 to 100°C) toluene, which might include a smaller or higher amount of TiCl 4 in it.
  • the amount of TiCl 4 can vary from a few vol% to more than 50-vol%, such as from 5-vol% to 50-vol%, preferably from 5 to 15-vol%. It is also possible that at least one wash is done with 100-vol% TiCl 4 .
  • One or several further washes after aromatic and/ or TiCl 4 washes can be run with aliphatic hydrocarbons of 4 to 8 carbon atoms. Preferable these latter washings are performed with heptane and/or pentane. Washings can be done with hot (e.g. 90°C) or cold (room temperature) hydrocarbons or combinations thereof. It is also possible that all washings will be done with the same solvent, e.g. toluene.
  • the washing can be optimized to give a catalyst component with novel and desirable properties.
  • It can further be dried, as by evaporation or flushing with nitrogen or it can be slurred to an oily liquid without any drying step.
  • a reducing agent which decreases the amount of titanium present in said solidified particles of the olefin polymerisation catalyst component being present in the oxidation state +4, can be added.
  • Suitable reducing agents are aluminium alkyl compounds, aluminium alkyl alkoxy compounds as well as magnesium compounds as defined in the present specification.
  • Suitable aluminium compounds have a general formula AlR 3-n X n , wherein R stands for a straight chain or branched alkyl or alkoxy group having 1 to 20, preferably 1 to 10 and more preferably 1 to 6 carbon atoms, X independently represents a residue selected from the group of halogen, preferably chloride, and n stands for 0, 1 or 2. At least one of the R residues has to be an alkyl group.
  • the compound can be added as an optional compound to the catalyst component synthesis and brought into contact with the droplets of the dispersed phase of the agitated emulsion before recovering the solidified particles in step (e2).
  • the Al compound can be added at any step (b2) to (d2), or during the washing step as described above, however, before step (e2).
  • aluminium alkyl and alkoxy compounds to be employed in accordance with the present invention are:
  • Suitable magnesium compounds are magnesium compounds as defined herein in connection with the complex of a Group 2 metal. The respective disclosure is incorporated herein by reference with respect to the magnesium compound to be added in accordance with the process of the present invention.
  • suitable magnesium compounds are dialkyl magnesium compounds or halogenated alkyl magnesium compounds of the general formula MgR 2-n X n , where each n is 0 or 1, and each R are same or different alkyl groups with 1 to 8 carbon atoms and X is halogen, preferably Cl.
  • One preferred magnesium compound is butyloctyl magnesium (commercially available under the trade name BOMAG), which is already preferably used in the preparation of the Mg complex.
  • the added amount of the optional Al compound depends on the desired degree of reduction of amount of titanium present in the solidified particles of the olefin polymerisation catalyst component being present in the oxidation state +4.
  • the preferred amounts of Al in the catalyst component depend to some extent on the Al compound, e.g. if an Al alkoxy compound is used, the preferred final Al amounts seem to be lower than if e.g. Al alkyl chloride compounds are used.
  • the final catalyst component particles have an Al content of 0.0 to 0.8 wt%, preferably 0.0 to 0.5 wt% or 0.0 to 0.4 wt%.
  • the magnesium compound to be added in accordance with the present invention is added in corresponding amounts.
  • the aluminium alkyl or alkoxy compound and the magnesium compound can be used alone or in combination.
  • the optional Al or Mg compound or a mixture thereof is preferably added before step (e2), more preferably during the washing step, which comprises at least one, preferably two and more preferably three washing procedures with the same or preferably different hydrocarbons as washing medium.
  • the aluminium alkyl or alkoxy compound and/ or magnesium compound to be used in the catalyst component preparation of the invention can be added to any of the washing mediums, which are, as described above, preferably toluene, heptane and/or pentane.
  • the procatalyst preparation according to the inventive method can be carried out batch-wise, it is also preferable and possible to prepare the catalyst component semi-continuously or continuously.
  • the solution of the complex of the group 2 metal and said electron donor which is prepared by reacting the compound of said metal with said electron donor in an organic liquid reaction medium, is mixed with at least one compound of a transition metal, which might be solved in the same or different organic liquid reaction medium.
  • the so obtained solution is then agitated, possibly in the presence of an emulsion stabilizer, and then the so-agitated emulsion is fed into a temperature gradient reactor, in which the emulsion is subjected a temperature gradient, thus leading to solidifying the droplets of a dispersed phase of the emulsion.
  • the optional TMA is preferably contained in the solution of the complex or added to the solution before feeding the agitated solution to the temperature gradient reactor.
  • an inert solvent in which the droplets are not soluble, can additionally be fed into that gradient reactor in order to improve the droplet formation and thus leading to a uniform grain size of the particles of the catalyst component, which are formed in the temperature gradient reactor when passing through said line.
  • additional solvent might be the same as the organic liquid reaction medium, which is used for preparing the solution of the complex of the group 2 metal as explained above in more detail.
  • the solidified particles of the olefin polymerisation catalyst component can subsequently be recovered by an in-stream filtering unit and then, optionally after some additional washing and drying steps in order to remove unreacted starting components, can be stored for further use.
  • the catalyst can be fed after washing steps into the olefin polymerisation reactor, so that a continuous preparation and feed to the reactor is guaranteed. It is also possible to mix the solidified and washed catalyst component with an oily fluidic liquid and store and use the catalyst component as catalyst component-oil slurry. In this way the drying steps can be avoided, which might be sometimes detrimental to the catalyst components morphology.
  • This oil-slurry method is described in general in EP-A-1489110 of the applicant, incorporated herein by reference.
  • the formation of the solidified particles could be carried out in the temperature gradient line in the kind of pipe reactor, which is sufficiently long and which is subjected said temperature gradient from the starting temperature in the lower range of 20 to 80°C up to a "solidifying" temperature of 70 to 150°C.
  • the temperature gradient is preferably obtained by means of heating the pipe reactor from the outside by applying normal heaters, microwaves, etc.
  • a filtering unit might preferably be used for filtering the solidified particles from the solvent stream.
  • various drums and sieving systems can be used, depending on the specific particle sizes.
  • a filtering unit might preferably be used for filtering the solidified particles from the solvent stream.
  • various drums and sieving systems can be used, depending on the specific particle sizes.
  • the finally obtained solid catalyst component is desirably in the form of particles having generally an average size range, determined by using a Coulter Counter LS200 at room temperature (20°C) with n-heptane as medium, of 2 to 500 ⁇ m, preferably 5 to 200 ⁇ m and more preferably 10 to 100, even an average size range of 20 to 60 ⁇ m is possible.
  • the particle size distribution, measured by Coulter method and defined as SPAN of the catalysts of the invention depends on the way of preparation. With the emulsion/solidification method the particle size distribution is usually lower than with the precipitation method. Nevertheless it is desired that the particle size distribution of the solid catalyst components prepared according to the precipitation method is as low as possible and even more preferred similar to that of solid catalyst components prepared according to the emulsion/solidification method.
  • the particle size distribution is in the range of 0.5 to at most 4.0, more preferable from 0.5 to at most 3.0 and even more preferably 0.5 to at most 2.0.
  • SPAN is defined as d 90 ⁇ m ⁇ d 10 ⁇ m d 50 ⁇ m where d90 indicates the particle diameter al 90% cumulative size, d10 indicates the particle diameter at 10% cumulative size, and d50 indicates the particle diameter at 50% cumulative size.
  • Catalysts prepared according to the method of the present invention have desired morphology and particle size as well as particle size distribution and are suitable for producing polymers with the desired polymer properties.
  • catalyst component particles having desired morphology and particle size as well as particle size distribution can be obtained by a common mechanism either via the precipitation or via the emulsion/solidification way of preparing Ziegler-Natta (ZN) type catalysts, and are suitable for use in olefin polymerisation, like ethylene or propylene, in particular for propylene polymerisation, optionally with other co-monomers selected from C 2 - C 12 monomers, preferably C 2 - C 6 monomers.
  • ZN Ziegler-Natta
  • alkoxy compound (Ax) and (Bx) enables the preparation of the desired solid catalyst component particles allowing addition of phthalate free donors as such or prepared in situ, whereby the internal donors used according to the present invention show high chemical stability and are therefore less prone to undergo transesterificiation/decomposition during Mg-complex formation and catalyst preparation than other phthalate free internal donors, like optionally substituted maleates.
  • the catalyst components according to the invention have good morphology, good particle size distribution and result in polymerisation catalysts having highly suitable polymerisation activities. According to the replica effect, the polymer particles produced by using the inventive catalyst components have good morphological properties, too. Not only the catalyst morphology, but also the catalyst composition, is of importance in getting the desired properties for the polymers. As indicated earlier in this application such desired properties are good hydrogen response as well as low randomness.
  • the catalysts of the invention have, as mentioned above, a Group 4 metal, preferably Ti content in the range of 1.0 to 10.0 wt%, preferably 1.5 to 7.5 wt% and more preferably 2.0 to 5.0 wt%; a Group 2 metal, preferably Mg content in the range of 6.0 to 22.0 wt%, preferably 7.0 to 20.0 wt% and more preferably 7.5 to 18.0 wt%; an Al content in the range of 0.0 to 0.8 wt%, preferably 0.0 to 0.5 wt% and more preferably 0.0 to 0.4 wt%.
  • the amount of Ti, Mg and Al is determined by ICP Analysis as described in the Experimental Part.
  • the amount of internal donor is in the range of 5.0 to 65.0 wt%, preferably 10.0 to 60.0 wt% and more preferably 20.0 to 58.0 wt% and is normally determined by HPLC or GC.
  • the inventive catalyst component preparation is based on a liquid/liquid two-phase system (emulsion/solidification method) or on the precipitation method where in both cases no separate external carrier materials such as silica or MgCl 2 are needed in order to get solid catalyst particles.
  • Polymerisation processes where the catalyst components of the invention are useful comprise at least one polymerisation stage, where polymerisation is typically carried out in solution, slurry, bulk or gas phase.
  • the polymerisation process comprises additional polymerisation stages or reactors.
  • the process contains at least one bulk reactor zone and at least one gas phase reactor zone, each zone comprising at least one reactor and all reactors being arranged in cascade.
  • the polymerisation process for polymerising olefins, in particular propylene optionally with comonomers, like ethylene or other alpha-olefins comprises at least one bulk reactor and at least one gas phase reactor arranged in that order.
  • the process comprises one bulk reactor and at least two, e.g.
  • the process may further comprise pre- and post reactors.
  • Pre-reactors comprise typically prepolymerisation reactors. In these kinds of processes use of higher polymerisation temperature (70 °C or higher, preferably 80°C or higher, even 85 °C or higher) either in some or all reactors of the reactor cascade, is preferred in order to achieve some specific properties to the polymers.
  • the catalyst system used comprises in addition to the catalyst components in form of solid particles as described above an organometallic cocatalyst.
  • the cocatalyst from the group consisting of trialkylaluminium, like triethylaluminium (TEA), triisobutylaluminium, tri-n-butylaluminium; dialkyl aluminium chloride, like dimethyl- or diethyl aluminium chloride; and alkyl aluminium sesquichloride. More preferably the cocatalyst is triethylaluminium or diethylaluminium chloride, most preferably triethylaluminium is used as cocatalyst.
  • TAA triethylaluminium
  • one or more external donor are used, which may be typically selected e.g. from silanes or any other well known external donors in the field.
  • External donors are known in the art and are used as stereoregulating agent in propylene polymerisation.
  • the external donors are preferably selected from hydrocarbyloxy silane compounds, amino silane compounds and hydrocarbyloxy alkane compounds.
  • Typical hydrocarbyloxy silane compounds have the formula (II) R 7 p Si(OR 8 ) 4-p (II) wherein
  • the alkoxy silane compound having the formula (II) is dicyclopentyl dimethoxy silane or cyclohexylmethyl dimethoxy silane.
  • Typical amino silane compounds have the formula (III) Si(OR 9 ) 3 (NR 10 R 11 ) wherein R 9 is a hydrocarbon group having 1 to 6 carbon atoms, R 10 is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen atom, and R 11 is a hydrocarbon group having 1 to 12 carbon atoms.
  • these compounds have the formula (IV) Si(OCH 2 CH 3 ) 3 (NR 10 R 11 ) Wherein R 10 and R 11 are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • R 10 and R 11 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert.-butyl, tert.-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl. More preferably both R 10 and R 11 are the same and have 1 to 6 carbon atoms, yet more preferably both R 10 and R 11 are a C 1 -C 4 -alkyl group.
  • the external donor represented by the formula (III) or (IV) is Diethyl aminotriethoxy silane.
  • the external donor used for the catalyst system is therefore preferably diethyl aminotriethoxy silane, dicyclopentyl dimethoxy silane or cyclohexyl methyldimethoxy silane.
  • SPAN is defined as follows: d 90 ⁇ m ⁇ d 10 ⁇ m d 50 ⁇ m
  • the elemental analysis of a catalyst was performed by taking a solid sample of mass, M, cooling over dry ice. Samples were diluted up to a known volume, V, by dissolving in nitric acid (HN0 3 , 65 %, 5 % of V) and freshly deionised (DI) water (5 % of V). The solution was further diluted with DI water up to the final volume, V, and left to stabilize for two hours.
  • nitric acid HN0 3 , 65 %, 5 % of V
  • DI freshly deionised
  • Thermo Elemental iCAP 6300 Inductively Coupled Plasma - Optical Emission Spectrometer (ICP-OES) which was calibrated using a blank (a solution of 5 % HNO 3 ), and standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, Mg and Ti in solutions of 5 % HNO 3 .
  • a quality control sample (20 ppm Al, Mg and Ti in a solution of 5 % HNO 3 , 3 % HF in DI water) is run to confirm the reslope.
  • the QC sample is also run after every 5 th sample and at the end of a scheduled analysis set.
  • the content of Mg was monitored using the 285.213 nm line and the content for Ti using 336.121 nm line.
  • the content of aluminium was monitored via the 167.079 nm line, when Al concentration in ICP sample was between 0-10 ppm (calibrated only to 100 ppm) and via the 396.152 nm line for Al concentrations above 10 ppm.
  • the reported values are an average of three successive aliquots taken from the same sample and are related back to the original catalyst by inputting the original mass of sample and the dilution volume into the software.
  • the donor analysis of a catalyst was performed by taking a solid sample of mass, M, approximately 2 ml of solvent, dichloromethane, was added. Following this approximately 1 ml of deionised water was added to the vial. Finally, a known mass, N, of an internal standard, nonane, was added. The mixture was then sonicated for 15 min, to ensure full dissolution. After sonication the sample is left to settle into two phases and an aliquot of the organic phase is removed, this is then filtered through a 0.45 ⁇ m nylon filter into a vial suitable for the gas chromatography instrument.
  • the analysis is performed on a Perkin Elmer Auto System XL Gas Chromatograph containing a split loop injector and flame ionization detector.
  • the column is a DB-1, 30 m long with an inner diameter of 0.32 mm and a phase thickness of 0.25 ⁇ m.
  • the system stays at 40 °C for 5 minutes before ramping at 10 °C/min up to 250 °C, the system is kept at temperature for a further 4 minutes. If required the peak temperature could be raised to 300 °C.
  • Infrared (IR) spectroscopy was undertaken on Nicolet Magna IR Spectrometer 550. A 220-250 ⁇ m film was prepared from the polymer powder at 230°C followed by rapid cooling to room temperature. All IR analysis was done within two hours of film preparation. Quantitative comonomer contents were obtained using peak areas normalised to the peak height of an internal reference band calibrated to previous 13 C NMR results. Ethylene was quantified using the band at 733 cm -1 (baseline 690-780 cm -1 ) the reference band at 809 cm -1 (baseline 750-890 cm -1 ).
  • Randomness random ethylene ⁇ P ⁇ E ⁇ P ⁇ content / the total ethylene content ⁇ 100 % .
  • Example 1 (reference example):
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared according to Example 10 was used.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared according to Example 12 was used.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared according to Example 14 was used.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared according to Example 16 was used.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared according to Example 18 was used.
  • the temperature of the reaction mixture was then increased to 90°C over a period of 20 minutes (linear heat-up profile) and held at that level for 30 minutes with stirring. Afterwards stirring was stopped, and the reaction mixture was allowed to settle for 15 minutes at 90°C. After settling and removing of the supernatant liquid the solids underwent 3 washing steps:
  • the reactor temperature was increased to 70 °C during 7 minutes, followed by N 2 sparging for 20 minutes, to yield a brown, air sensitive powder.
  • a 5 litre stainless steel reactor was used for propylene polymerisations.
  • Half of the mixture was then added to the polymerisation reactor and the other half was mixed with about 20 mg of a catalyst. After additional 5 minutes the catalyst/TEA/donor/n-pentane mixture was added to the reactor.
  • the Al/Ti ratio was 250 mol/mol and the AI/DCDS ratio was 10 mol/mol.
  • 200 mmol hydrogen and 1400 g propylene were introduced into the reactor and the temperature was raised within ca 15 minutes to the polymerisation temperature (80 °C).
  • the polymerisation time after reaching polymerisation temperature was 60 minutes, after which the polymer formed was taken out from the reactor.
  • the catalysts according to the invention yield products with higher MFR which proves the better hydrogen response compared to the comparative catalyst.
  • the Al/Ti ratio was 150 mol/mol and the AI/DCDS ratio was 10 mol/mol.
  • 300 mmol hydrogen and 1400 g propylene were introduced into the reactor and the temperature was raised within ca 15 minutes to the polymerisation temperature (70 °C).
  • Ethylene feed was started 5 minutes after starting the temperature increase (at about 40°C) and ethylene was fed continuously throughout the polymerisation, in total 26.6 g.
  • the polymerisation time at 70°C was 60 minutes, after which the polymer formed was taken out from the reactor.
  • the yield was 484 g.
  • This example was done in accordance with example 22, except that the catalyst was the same as the catalyst described in example 19 with 2.68 wt% titanium, catalyst amount 18.1 mg, Al/Ti molar ratio was 250, AI/Do 10 mol/mol. The yield was 588 g.
  • This example was done in accordance with example 22, except that the catalyst was the same as the catalyst described in CE1 with 3.1 wt% titanium, catalyst amount 11.1 mg, TEAL amount 300 ⁇ l (Al/Ti molar ratio 305) and Al/Do molar ratio 10. The yield was 549 g.
  • This example was done in accordance with comparative example CE2, except that the catalyst was the same as the catalyst described in CE1 with 3.7 wt% titanium, TEAL amount 300 ⁇ l (Al/Ti 202 mol/mol), Al/Do 10. The yield was 414 g.
  • the catalysts according to the invention having benzoates as internal donor gave at least 3% lower randomness at the same C 2 -content than the catalysts of the comparative examples having a phthalate as internal donor.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared as described above was used.
  • the catalyst component was prepared as described in Example 8, except that the Mg-complex prepared as described above was used.
  • Peaks above 24 min are from transesterification/decomposition products, peaks below 12 min are solvent signals.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (15)

  1. Procédé pour préparer un composant de catalyseur de polymérisation d'oléfines sous la forme de particules solides, comprenant les étapes consistant à
    a) préparer une solution d'au moins un composé alcoxy (Ax) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 avec au moins un alcool monovalent (A), et d'au moins un composé alcoxy (Bx) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, ou une solution d'au moins un composé alcoxy (Ax) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un mélange d'alcool monovalent (A) avec un autre alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, dans un milieu réactionnel liquide organique,
    b) ajouter ladite solution à au moins un composé d'un métal de transition, et
    c) préparer les particules de composant de catalyseur solide,
    dans lequel un ester d'acide benzoïque de formule (I)
    Figure imgb0014
     dans laquelle R est un groupe alkyle en C1 à C12 linéaire ou ramifié, de préférence un groupe alkyle en C2 à C10 linéaire ou ramifié, plus préférablement un groupe alkyle en C4 à C9 linéaire ou ramifié, et le plus préférablement un groupe alkyle en C6 à C8 ramifié, et
    R' est H ou un groupe alkyle en C1 à C12 linéaire ou ramifié, de préférence un groupe alkyle en C2 à C10 linéaire ou ramifié, plus préférablement un groupe alkyle en C4 à C8 linéaire ou ramifié, le groupe alkyle pouvant contenir un ou plusieurs hétéroatome(s) choisi(s) parmi O, N ou S, de préférence parmi O ou N, plus préférablement O, dans la chaîne alkyle, ou pouvant être substitué par un ou plusieurs substituant(s) choisi(s) parmi =O, les halogènes ou les radicaux aryle en C6 à C14 éventuellement substitués, ou un précurseur correspondant, ou bien
    un dibenzoate d'alkylèneglycol choisi parmi le dibenzoate d'éthylèneglycol, le dibenzoate de 1,2-propylèneglycol et le dibenzoate de 1,3-propylèneglycol, ou un précurseur correspondant, ou leurs mélanges, est ajouté en tant que donneur interne à n'importe quelle étape avant l'étape c).
  2. Procédé selon la revendication 1, dans lequel les alcools monovalents (A) sont ceux de formule ROH dans laquelle R est un alkyle en C1 à C20 linéaire ou ramifié.
  3. Procédé selon la revendication 1 ou 2, dans lequel, dans l'alcool (B), l'autre groupe oxygéné est un fragment éther.
  4. Procédé selon la revendication 1, 2 ou 3, dans lequel l'alcool (B) est un monoéther de glycol en C2 à C4, et dans lequel le fragment éther comprend de 2 à 18 atomes de carbone.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit métal du Groupe 2 est le magnésium.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel ledit métal de transition est un métal du Groupe 4 et/ou un métal du Groupe 5, de préférence Ti.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la préparation du composant de catalyseur de polymérisation d'oléfines sous la forme de particules solides comprend les étapes consistant à
    (a1) préparer une solution (S1) d'au moins un composé alcoxy (Ax), qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 avec au moins un alcool monovalent (A), et d'au moins un composé alcoxy (Bx) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, ou une solution d'au moins un composé alcoxy (Ax) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un mélange d'alcool monovalent (A) avec un autre alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, et d'un donneur d'électron de formule (I) ou d'un dibenzoate d'alkylèneglycol choisi parmi le dibenzoate d'éthylèneglycol, le dibenzoate de 1,2-propylèneglycol et le dibenzoate de 1,3-propylèneglycol ou un précurseur correspondant de celui-ci dans un milieu réactionnel liquide organique (OM1),
    (b1) combiner ladite solution (S1) avec au moins un composé de métal de transition (CT), et
    (c1) précipiter ledit composant de catalyseur sous la forme d'une particule solide, et
    (d1) récupérer les particules solidifiées du composant de catalyseur de polymérisation d'oléfines.
  8. Procédé selon la revendication 7, dans lequel l'addition de la solution (S1) à l'au moins un composé de métal de transition (CT) dans l'étape (b1) est effectuée à une température située dans la plage allant de 50 à 110°C, température à laquelle l'au moins un composé de métal de transition (CT) est sous une forme liquide, ce qui a pour résultat la précipitation desdits composants de catalyseur solides, un tensioactif pouvant être ajouté à l'étape (a1) ou à l'étape (b1).
  9. Procédé selon la revendication 7, dans lequel la solution (S1) est mélangée avec au moins un composé de métal de transition (CT) sous forme liquide à une température d'environ -20°C à environ 30°C et les composants de catalyseur solides sont précipités par élévation lente subséquente de la température à une température située dans la plage allant de 50 à 110°C, la vitesse de montée en température étant située dans la plage allant de 0,1°C à 30°C par minute, de préférence de 0,5 à 10°C par minute, et un tensioactif étant ajouté à la solution (S1) avant l'étape (b1).
  10. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel la préparation du composant de catalyseur sous la forme de particules solides comprend les étapes consistant à
    (a2) préparer une solution d'au moins un composé alcoxy (Ax), qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 avec au moins un alcool monovalent (A), et d'au moins un composé alcoxy (Bx) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, ou une solution d'au moins un composé alcoxy (Ax) qui est le produit de la réaction d'au moins un composé d'un métal du Groupe 2 et d'un mélange d'alcool monovalent (A) avec un autre alcool (B) comprenant, en plus du fragment hydroxyle, au moins un autre groupe oxygéné qui est différent d'un fragment hydroxyle, et d'un donneur d'électron de formule (I) ou d'un dibenzoate d'alkylèneglycol choisi parmi le dibenzoate d'éthylèneglycol, le dibenzoate de 1,2-propylèneglycol et le dibenzoate de 1,3-propylèneglycol ou un précurseur de celui-ci dans un milieu réactionnel liquide organique,
    (b2) ajouter ladite solution à au moins un composé d'un métal de transition pour produire une émulsion, dont la phase dispersée est sous la forme de gouttelettes et contient plus de 50 % en moles du métal du Groupe 2 dans ledit composé alcoxy (Ax),
    (c2) agiter l'émulsion afin de maintenir les gouttelettes de ladite phase dispersée dans ladite plage de taille moyenne prédéterminée de 2 à 500 µm,
    (d2) solidifier lesdites gouttelettes de la phase dispersée,
    (e2) récupérer les particules solidifiées du composant de catalyseur de polymérisation d'oléfines.
  11. Procédé selon la revendication 10, caractérisé en ce qu'il est effectué en continu.
  12. Particules du composant de catalyseur pouvant être obtenu selon l'une quelconque des revendications 1 à 11.
  13. Particules du composant de catalyseur selon la revendication 12, ayant une granulométrie moyenne (déterminée par utilisation d'un compteur Coulter LS200 à 25°C dans du n-heptane) située dans la plage allant de 10 à 100 µm.
  14. Catalyseur de polymérisation d'oléfines comprenant des particules du composant de catalyseur selon la revendication 12 ou 13 et un co-catalyseur, de préférence un co-catalyseur alkyl-aluminium et éventuellement un donneur d'électron externe.
  15. Utilisation du catalyseur tel que défini dans la revendication 14 pour la polymérisation d'oléfines, en particulier d'α-oléfines en C2 à C10, de préférence l'éthylène ou le propylène, éventuellement avec des co-monomères, choisis parmi les monomères en C2 à C12.
EP11196164.5A 2011-12-30 2011-12-30 Composant de catalyseur Not-in-force EP2610272B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11196164.5A EP2610272B1 (fr) 2011-12-30 2011-12-30 Composant de catalyseur
PCT/EP2012/076052 WO2013098138A1 (fr) 2011-12-30 2012-12-19 Composant catalytique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11196164.5A EP2610272B1 (fr) 2011-12-30 2011-12-30 Composant de catalyseur

Publications (2)

Publication Number Publication Date
EP2610272A1 EP2610272A1 (fr) 2013-07-03
EP2610272B1 true EP2610272B1 (fr) 2017-05-10

Family

ID=47435954

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11196164.5A Not-in-force EP2610272B1 (fr) 2011-12-30 2011-12-30 Composant de catalyseur

Country Status (2)

Country Link
EP (1) EP2610272B1 (fr)
WO (1) WO2013098138A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107936154A (zh) * 2017-12-01 2018-04-20 中国石油天然气股份有限公司 一种烷氧基镁催化剂载体及其制备方法和应用
US10472509B2 (en) 2015-11-17 2019-11-12 Borealis Ag High flow TPO composition with excellent balance in mechanical properties for automotive interior
US10851191B2 (en) 2015-06-30 2020-12-01 Borealis Ag Process for preparing propylene polymer compositions
US11098141B2 (en) 2015-12-21 2021-08-24 Borealis Ag Articles with improved optical properties
US11292858B2 (en) 2016-12-29 2022-04-05 Borealis Ag Polypropylene composition combining low sealing initiation temperature and high melting temperature
US11440300B2 (en) 2018-07-23 2022-09-13 Borealis Ag Multilayer polyproylene film

Families Citing this family (122)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6216887B2 (ja) 2013-08-14 2017-10-18 ボレアリス・アクチェンゲゼルシャフトＢｏｒｅａｌｉｓ Ａｇ 低温における耐衝撃性が改善されたプロピレン組成物
CN105452363B (zh) 2013-08-21 2018-06-12 博里利斯股份公司 具有高刚性和韧性的高流动聚烯烃组合物
BR112016003128B1 (pt) 2013-08-21 2021-08-24 Borealis Ag Composição de poliolefina de alto fluxo com alta rigidez e resistência e artigos automotivos
PT2853563T (pt) 2013-09-27 2016-07-14 Borealis Ag Filmes adequados para processamento de bopp a partir de polímeros com xs elevada e tm elevado
EP2860031B1 (fr) 2013-10-11 2016-03-30 Borealis AG Film orienté dans le sens machine pour étiquettes
US10519259B2 (en) 2013-10-24 2019-12-31 Borealis Ag Low melting PP homopolymer with high content of regioerrors and high molecular weight
ES2574428T3 (es) 2013-10-24 2016-06-17 Borealis Ag Artículo moldeado por soplado basado en copolímero al azar bimodal
US9670293B2 (en) 2013-10-29 2017-06-06 Borealis Ag Solid single site catalysts with high polymerisation activity
WO2015075054A1 (fr) 2013-11-22 2015-05-28 Borealis Ag Homopolymère de propylène à faible émission
BR112016009549B1 (pt) 2013-11-22 2021-07-27 Borealis Ag Homopolímero de propileno de baixa emissão com alto índice de fluidez
CN105793298B (zh) 2013-12-04 2019-06-28 博里利斯股份公司 用于熔喷纤维的不含邻苯二甲酸酯的pp均聚物
WO2015091839A1 (fr) 2013-12-18 2015-06-25 Borealis Ag Film bopp présentant un meilleur équilibre rigidité/résistance
EP3094660B1 (fr) 2014-01-17 2018-12-19 Borealis AG Procédé de préparation de copolymères de propylène/1-butène
JP2017508032A (ja) 2014-02-06 2017-03-23 ボレアリス エージー 高衝撃強さを有する軟質コポリマー
EP3102634B1 (fr) 2014-02-06 2019-12-04 Borealis AG Copolymères d'impact souple et transparent
EP2907841A1 (fr) 2014-02-14 2015-08-19 Borealis AG Composition de polypropylène
EP2947118B1 (fr) 2014-05-20 2017-11-29 Borealis AG Composition de polypropylène pour des applications d'intérieur d'automobile
ES2676219T3 (es) 2014-06-27 2018-07-17 Borealis Ag Componente de catalizador para la preparación de poliolefinas nucleadas
PL2960279T3 (pl) * 2014-06-27 2018-08-31 Borealis Ag Kompozycja polipropylenu poddana nukleacji
ES2929284T3 (es) 2014-06-27 2022-11-28 Borealis Ag Proceso mejorado para preparar un componente catalizador de polimerización de olefinas en partículas
WO2016008749A1 (fr) 2014-07-15 2016-01-21 Borealis Ag Homopolymères nucléés de pp exempts de phtalates pour des fibres soufflées à l'état fondu
EP3006472A1 (fr) 2014-10-07 2016-04-13 Borealis AG Procédé pour la préparation d'un polypropylène nucléé alpha
EP3015504A1 (fr) 2014-10-27 2016-05-04 Borealis AG Polypropylène hétérophasique présentant une répartition de rigidité et une résistance à l'impact améliorées en cas de perforation
EP3015503A1 (fr) 2014-10-27 2016-05-04 Borealis AG Polypropylène hétérophasique avec un équilibre amélioré en termes de rigidité/impact
US9890274B2 (en) 2014-10-27 2018-02-13 Borealis Ag Heterophasic polypropylene with improved impact strength/stiffness balance, improved powder flowability, reduced emissions and low shrinkage
EP3018155A1 (fr) 2014-11-05 2016-05-11 Borealis AG Polypropylène ramifié pour des applications de films
EP3018153B1 (fr) 2014-11-05 2019-02-27 Borealis AG Polypropylène ramifié à chaîne longue pour utilisation dans des mousses
ES2717433T3 (es) 2014-11-05 2019-06-21 Borealis Ag Polipropileno ramificado de cadena larga para la aplicación en películas
CN107075207B (zh) 2014-11-19 2018-07-27 博里利斯股份公司 基于丙烯均聚物的注射成型制品
ES2790649T3 (es) 2014-12-08 2020-10-28 Borealis Ag Procedimiento para producir gránulos de copolímeros de propileno
DK3034522T3 (en) 2014-12-15 2019-04-15 Borealis Ag Use of a polypropylene composition
EP3237466B1 (fr) 2014-12-22 2023-05-03 Borealis AG Procédé de production de polypropylène
CN107406645A (zh) 2015-02-20 2017-11-28 北欧化工股份公司 制备多相丙烯共聚物的方法
ES2772677T3 (es) 2015-02-25 2020-07-08 Borealis Ag Composición de copolímero de propileno con propiedades mecánicas a largo plazo mejoradas
EP3307821A1 (fr) 2015-06-12 2018-04-18 Borealis AG Procédé de production de compositions de polymère de polypropylène
ES2778674T3 (es) 2015-07-08 2020-08-11 Borealis Ag Copolímero de propileno aleatorio heterofásico con claridad mejorada
ES2683493T3 (es) 2015-07-08 2018-09-26 Borealis Ag Polipropileno heterofásico con fluidez mejorada en forma de polvo, emisiones reducidas y baja contracción
ES2637434T5 (es) 2015-07-08 2020-07-06 Borealis Ag Tubo elaborado de una composición de polipropileno heterofásico
US10870718B2 (en) 2015-07-16 2020-12-22 Borealis Ag Catalyst component
US10081726B2 (en) 2015-08-14 2018-09-25 Borealis Ag Composite comprising a cellulose-based filler
BR112018009394B1 (pt) 2015-11-17 2022-05-03 Borealis Ag Copolímero de propileno heterofásico, composição de poliolefina, artigo automotivo, processo para preparação de uma composição de poliolefina, e, uso de um copolímero de propileno heterofásico
BR112018009066B1 (pt) 2015-11-17 2022-03-03 Borealis Ag Copolímero de propileno heterofásico, composição de poliolefina, artigo automotivo, processo para preparação de uma composição de poliolefina, e, uso de um copolímero de propileno heterofásico
PT3184587T (pt) 2015-12-21 2020-06-02 Borealis Ag Artigos extrudidos com propriedades óticas melhoradas
EP3187512A1 (fr) 2015-12-31 2017-07-05 Borealis AG Procédé de production de compositions de copolymères de propylène
ES2900514T3 (es) 2016-01-04 2022-03-17 Borealis Ag Telas no tejidas unidas por hilado fabricadas a partir de homopolímeros de PP exentos de ftalato
US10647838B2 (en) 2016-01-29 2020-05-12 Borealis Ag Heterophasic propylene copolymer with low shrinkage
US10759931B2 (en) 2016-03-04 2020-09-01 Borealis Ag High flow heterophasic polyolefin compositions having improved stiffness/impact balance
CN108884191B (zh) 2016-04-13 2021-10-22 博里利斯股份公司 基于丙烯均聚物的注射成型制品
EP3246358A1 (fr) 2016-05-18 2017-11-22 Borealis AG Copolymères de propylène souple et transparent
ES2774737T3 (es) 2016-05-18 2020-07-22 Borealis Ag Composición blanda de polipropileno
DK3255071T3 (en) * 2016-06-06 2024-04-02 Borealis Ag Polypropylene composition with improved heat resistance
DK3257988T3 (da) 2016-06-13 2019-11-04 Borealis Ag Smelteblæste baner af høj kvalitet med forbedrede barriereegenskaber
ES2968167T3 (es) 2016-06-16 2024-05-08 Borealis Ag Terpolímeros de propileno-etileno-butileno nucleados y artículos moldeados fabricados a partir de los mismos
EP3257878B1 (fr) 2016-06-16 2023-05-03 Borealis AG Copolymères de propylène-butylène avec des propriétés optiques et mécaniques améliorées et une meilleure aptitude au traitement ainsi que des articles fabriqués à partir de ceux-ci
EP3263640A1 (fr) 2016-06-28 2018-01-03 Borealis AG Composition de polypropylène souple et transparent
EP3263641B1 (fr) 2016-06-29 2021-03-24 Borealis AG Composite de polypropylène renforcé de fibres
CN111205559B (zh) 2016-08-03 2022-10-21 博里利斯股份公司 纤维增强的聚丙烯复合材料
CN109790230A (zh) 2016-10-12 2019-05-21 北欧化工公司 具有良好韧性的β-成核的丙烯三元共聚物组合物
EP3309212B1 (fr) 2016-10-17 2018-12-12 Borealis AG Composite de polypropylène renforcé de fibres
PL3309211T3 (pl) 2016-10-17 2019-05-31 Borealis Ag Kompozyt polipropylenowy wzmocniony włóknem
ES2975632T3 (es) 2016-10-25 2024-07-10 Borealis Ag Copolímeros de polipropileno heterofásicos de flujo elevado con propiedades mecánicas y ópticas mejoradas
ES2873505T3 (es) 2016-10-25 2021-11-03 Borealis Ag Composición de polipropileno heterofásico con propiedades ópticas y mecánicas mejoradas
ES2870199T3 (es) 2016-12-09 2021-10-26 Borealis Ag Estructura no tejida de múltiples capas
ES2952512T3 (es) 2016-12-15 2023-10-31 Borealis Ag Composición de polipropileno con excelente adhesión de la pintura
ES2940416T3 (es) 2016-12-29 2023-05-08 Borealis Ag Composición de polipropileno, que combina baja temperatura de inicio del sellado y alta temperatura de fusión
TWI673291B (zh) 2016-12-29 2019-10-01 奧地利商柏列利斯股份公司 用於製備聚丙烯組成物的方法
WO2018185024A1 (fr) 2017-04-04 2018-10-11 Borealis Ag Composition de polypropylène souple avec des propriétés améliorées
EP3395377A1 (fr) 2017-04-28 2018-10-31 Borealis AG Composition de polypropylène souple dotée de propriétés améliorées
WO2018210477A1 (fr) 2017-05-18 2018-11-22 Borealis Ag Copolymères nucléés en c3c4 et terpolymères nucléés en c3c4c2
US11390700B2 (en) 2017-05-18 2022-07-19 Borealis Ag Propylene-ethylene random copolymer with improved irradiation resistance
US20210115235A1 (en) 2017-05-18 2021-04-22 Borealis Ag Heterophasic polyolefin composition with excellent optical properties
ES2960629T3 (es) 2017-06-29 2024-03-05 Borealis Ag Procedimiento para la preparación de una composición de polipropileno
ES2959196T3 (es) 2017-06-29 2024-02-21 Borealis Ag Composición de polipropileno con excelente rendimiento al impacto
EA201992724A1 (fr) 2017-06-29 2020-06-04
EP3421538B1 (fr) 2017-06-30 2021-03-17 Borealis AG Composition de polyoléfine ayant une excellente apparence de surface
EP3652247B2 (fr) 2017-07-14 2024-09-04 Borealis AG Composition de polypropylène
PT3447088T (pt) 2017-08-21 2020-02-03 Borealis Ag Composição de polipropileno
EP3453727A1 (fr) 2017-09-08 2019-03-13 Borealis AG Procédé de préparation de compositions de polypropylène
EP3456776B1 (fr) 2017-09-13 2019-12-11 Borealis AG Composition de polypropylène
US20200308385A1 (en) 2017-09-20 2020-10-01 Borealis Ag Polypropylene composition
EP3700943A1 (fr) 2017-10-24 2020-09-02 Borealis AG Catalyseurs
EP3489297B1 (fr) 2017-11-28 2021-08-04 Borealis AG Composition polymère présentant une meilleure adhérence de la peinture
ES2890961T3 (es) 2017-11-28 2022-01-25 Borealis Ag Composición de polímero con adherencia de la pintura mejorada
PL3495421T5 (pl) 2017-12-05 2024-06-17 Borealis Ag Kompozycja polipropylenowa wzmocniona włóknami
ES2837424T3 (es) 2017-12-05 2021-06-30 Borealis Ag Composición de polipropileno reforzada con fibra
PL3495423T3 (pl) 2017-12-05 2021-08-09 Borealis Ag Wyrób zawierający kompozycję polipropylenową wzmocnioną włóknami
WO2019115510A1 (fr) 2017-12-14 2019-06-20 Borealis Ag Procédé de préparation d'une composition de polypropylène
EP3732208A1 (fr) 2017-12-27 2020-11-04 Borealis AG Catalyseur de ziegler-natta et préparation correspondante
WO2019129650A1 (fr) 2017-12-28 2019-07-04 Borealis Ag Catalyseur et préparation associée
EP3505566A1 (fr) 2017-12-28 2019-07-03 Borealis AG Veste de câble
EP3506323B1 (fr) 2017-12-28 2023-06-14 Borealis AG Utilisation d'une gaine de câble
KR20200083636A (ko) 2018-01-05 2020-07-08 보레알리스 아게 개선된 밀봉 거동을 갖는 폴리프로필렌 조성물
EP3604425A1 (fr) 2018-07-31 2020-02-05 Borealis AG Composition de mousse de polypropylène comprenant des fibres polymères
EP3620487B1 (fr) 2018-09-06 2020-11-18 Borealis AG Composition à base de polypropylène à peignabilité améliorée
EP3620486B1 (fr) 2018-09-06 2020-11-18 Borealis AG Composition à base de polypropylène à peignabilité améliorée
EP3628693A1 (fr) 2018-09-28 2020-04-01 Borealis AG Procédé de production d'un copolymère de propylène hétérophasique présentant une grande fraction soluble à froid dans le xylène (xcs)
EP3856800A1 (fr) 2018-09-28 2021-08-04 Borealis AG Procédé de production d'un catalyseur ziegler-natta solide prépolymérisé
CN113166292A (zh) 2018-11-30 2021-07-23 博里利斯股份公司 洗涤工艺
EP3898720A1 (fr) 2018-12-21 2021-10-27 Borealis AG Catalyseur et sa préparation
EP3670547B1 (fr) 2018-12-21 2023-06-07 Borealis AG Composition de polypropylène pour couche d'étanchéité de film
EP3917979A1 (fr) 2019-02-01 2021-12-08 Borealis AG Terpolymère bimodal
ES2970193T3 (es) 2019-02-01 2024-05-27 Borealis Ag Composición de polipropileno
EP3715410B1 (fr) 2019-03-29 2024-07-17 Borealis AG Composition contenant un matériau recyclé pour tuyaux
US20220227030A1 (en) 2019-04-29 2022-07-21 Borealis Ag Process for preparing a cap or closure
WO2020245251A2 (fr) 2019-06-05 2020-12-10 Borealis Ag Film en polypropylène multicouche
EP3994187A1 (fr) 2019-07-04 2022-05-11 Borealis AG Composition de polymère de propylène ramifié à chaîne longue
EP4017916B1 (fr) 2019-08-19 2023-05-24 Borealis AG Mélanges de polypropylène-polyéthylène présentant des propriétés améliorées
US11214633B2 (en) 2019-09-10 2022-01-04 Braskem America, Inc. Ziegler-Natta catalyst systems and methods of controlling particle size
ES2948965T3 (es) 2019-10-23 2023-09-22 Borealis Ag Composición de polipropileno con una capacidad de procesamiento y resistencia al impacto mejoradas
EP3838971B1 (fr) 2019-12-16 2023-02-08 Abu Dhabi Polymers Co. Ltd (Borouge) Llc. Composition de polypropylène expansé appropriée pour feuilles et articles
EP3875503A1 (fr) 2020-03-02 2021-09-08 Borealis AG Catalyseur et sa préparation
EP3912810B1 (fr) 2020-05-18 2022-08-10 Borealis AG Composition de polypropylène
EP3945112A1 (fr) 2020-07-31 2022-02-02 Borealis AG Composition de polypropylène multimodal présentant une rigidité et une fluidité élevées et son procédé de production
WO2022106710A1 (fr) 2020-11-23 2022-05-27 Borealis Ag Mélange en réacteur in situ d'un polypropylène nucléé obtenu par catalyse de ziegler-natta et d'un polypropylène obtenu par catalyse par métallocènes
EP4330001A1 (fr) 2021-04-30 2024-03-06 Borealis AG Composition de polymère comprenant du polypropylène et une résine hydrocarbonée
US20240279451A1 (en) 2021-06-09 2024-08-22 Borealis Ag Polypropylene composition
WO2023012159A1 (fr) 2021-08-04 2023-02-09 Borealis Ag Structure de non-tissé multicouches
ES2982603T3 (es) 2021-08-31 2024-10-17 Borealis Ag Una mezcla de homopolímero y copolímero aleatorio con un equilibrio beneficioso de propiedades ópticas y mecánicas
EP4416194A1 (fr) 2021-10-14 2024-08-21 Borealis AG Procédé de formation d'un composant de catalyseur ziegler-natta
WO2023180266A1 (fr) 2022-03-23 2023-09-28 Borealis Ag Composition de polypropylène pour applications automobiles
WO2023180272A1 (fr) 2022-03-23 2023-09-28 Borealis Ag Composition de polypropylène à haut débit pour applications de moulage par injection
EP4375328A1 (fr) 2022-11-23 2024-05-29 Borealis AG Composition de polypropylène pour applications automobiles

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55135105A (en) * 1979-04-10 1980-10-21 Mitsui Petrochem Ind Ltd Titanium catalyst component for olefin polymerization
US4548915A (en) * 1984-04-10 1985-10-22 Shell Oil Company Olefin polymerization catalyst composition
JP3471099B2 (ja) 1994-11-25 2003-11-25 昭和電工株式会社 オレフィン重合用触媒担体の製造方法
US5955396A (en) 1995-10-17 1999-09-21 Bp Amoco Corporation Morphology-controlled olefin polymerization catalyst formed from an emulsion
WO1999033883A1 (fr) 1997-12-23 1999-07-08 Borealis Technology Oy Composant catalytique comprenant du magnesium, du titane, un halogene et un donneur d'electrons, sa preparation et son utilisation
FI981717A (fi) 1998-08-07 2000-02-08 Borealis As Katalysaattorikomponentti, joka käsittää magnesiumia, titaania, halogeenia ja elektronidonorin, sen valmistus ja käyttö
FI981718A (fi) 1998-08-07 2000-02-08 Borealis As Katalysaattorikomponentti, joka käsittää magnesiumia, titaania, halogeenia ja elektrodonorin, sen valmistus ja käyttö
GB0001914D0 (en) 2000-01-27 2000-03-22 Borealis Polymers Oy Catalyst
ATE328912T1 (de) 2001-06-20 2006-06-15 Borealis Tech Oy Herstellung eines katalysatorbestandteils zur olefinpolymerisation
EP1403292B1 (fr) 2002-09-30 2016-04-13 Borealis Polymers Oy Procédé pour la préparation d'un catalyseur pour la polymérisation d'olefins avec une amélioration d'activité à haute temperature
ES2377948T3 (es) 2003-06-20 2012-04-03 Borealis Polymers Oy Procedimiento para la preparación de una composición de un catalizador para la polimerización de olefinas
US7135531B2 (en) 2004-01-28 2006-11-14 Basf Catalysts Llc Spherical catalyst for olefin polymerization
US7153803B2 (en) * 2004-06-28 2006-12-26 Engelhard Corporation High activity and good hydrogen response Ziegler-Natta polyethylene catalyst
ES2594859T3 (es) 2006-05-31 2016-12-23 Borealis Technology Oy Catalizador con componente de Al-alcoxilo
EP1862480B1 (fr) 2006-05-31 2016-07-27 Borealis Technology Oy Procédé pour la préparation d'un catalyseur pour la polymérisation d'oléfines avec une amélioration d'activité à haute température

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10851191B2 (en) 2015-06-30 2020-12-01 Borealis Ag Process for preparing propylene polymer compositions
US10472509B2 (en) 2015-11-17 2019-11-12 Borealis Ag High flow TPO composition with excellent balance in mechanical properties for automotive interior
US11098141B2 (en) 2015-12-21 2021-08-24 Borealis Ag Articles with improved optical properties
US11292858B2 (en) 2016-12-29 2022-04-05 Borealis Ag Polypropylene composition combining low sealing initiation temperature and high melting temperature
CN107936154A (zh) * 2017-12-01 2018-04-20 中国石油天然气股份有限公司 一种烷氧基镁催化剂载体及其制备方法和应用
US11084890B2 (en) 2017-12-01 2021-08-10 Petrochina Company Ltd. Magnesium alkoxide catalyst support and the preparation method and use thereof
US11440300B2 (en) 2018-07-23 2022-09-13 Borealis Ag Multilayer polyproylene film

Also Published As

Publication number Publication date
EP2610272A1 (fr) 2013-07-03
WO2013098138A1 (fr) 2013-07-04

Similar Documents

Publication Publication Date Title
EP2610272B1 (fr) Composant de catalyseur
EP2610270B1 (fr) Composant de catalyseur
EP2610271B1 (fr) Préparation de catalyseurs ZN PP sans phthalate
EP2610273B1 (fr) Composant de catalyseur
US10113021B2 (en) Propylene random copolymer
EP2746300B1 (fr) Procédé de production d'un procatalyseur ziegler-natta pour la polymérisation d'éthylène
EP2960257B1 (fr) Procédé amélioré de préparation d'un composant de catalyseur de polymérisation d'oléfine particulaire
EP1862479A1 (fr) Catalyseur pour la polymérisation d'oléfines
US8592536B2 (en) Catalyst preparation using H2
EP3837290B1 (fr) Composants et catalyseurs pour la polymérisation des oléfines

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20131220

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20140218

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C08F 10/06 20060101AFI20161110BHEP

Ipc: C08F 4/651 20060101ALI20161110BHEP

Ipc: C08F 4/655 20060101ALI20161110BHEP

Ipc: C08F 110/06 20060101ALI20161110BHEP

Ipc: C08F 4/654 20060101ALI20161110BHEP

INTG Intention to grant announced

Effective date: 20161207

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 892248

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170515

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011037759

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170510

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 892248

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170811

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170810

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170910

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170810

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011037759

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20180213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20171230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171230

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171230

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180831

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180102

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171230

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171230

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111230

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170510

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20221213

Year of fee payment: 12

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230602

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011037759

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240702